Density Functional Theory Investigation on the Reaction Mechanisms of Ti(^3F)with CH2Cl2 and CHCl3 to CH2=TiCl2 and HC÷TiCl3  

作　　者：CHENG Xue-Li 

机构地区：[1](School of Chemistry and Chemical Engineering,Taishan University,Tai'an,Shandong 271021,China

出　　处：《Chinese Journal of Structural Chemistry》2016年第2期193-198,共6页结构化学（英文）

基　　金：financially supported by the National Natural Science Foundation of China(11174215);Natural Science Foundation of Shandong Province(ZR2012BL10);the University Science and Technology Project of Shandong Province(No.J13LD05)

摘　　要：The reaction mechanisms of Ti（~3F） ＋ CH2C12→CH2=TiCl2 and Ti（~3F） ＋ CHC13→HC÷TiCl3 were investigated with Gaussian 03 program package at the B3PW91/6-311＋＋G（d,p）level.The computational results revealed that：1） Both reaction systems are initiated by Ti（~3F） atom attacking the C atom of CH2C12 and CHCl3 to activate a C-Cl bond;2） Both reaction systems were carried out via triplet reaction channels;3） CH2=TiCl2 has singlet and triplet isomers,and the singlet one is more stable;4） The HOMO of CH2=TiCl2（S） illustrates a π-bonding interaction between C and Ti;5） Only singlet HC÷TiCl3 was located,and the Mulliken atomic spin densities show that the two single electrons are mostly on the C atom.The reaction mechanisms of Ti（~3F） ＋ CH2C12→CH2=TiCl2 and Ti（~3F） ＋ CHC13→HC÷TiCl3 were investigated with Gaussian 03 program package at the B3PW91/6-311＋＋G（d,p）level.The computational results revealed that：1） Both reaction systems are initiated by Ti（~3F） atom attacking the C atom of CH2C12 and CHCl3 to activate a C-Cl bond;2） Both reaction systems were carried out via triplet reaction channels;3） CH2=TiCl2 has singlet and triplet isomers,and the singlet one is more stable;4） The HOMO of CH2=TiCl2（S） illustrates a π-bonding interaction between C and Ti;5） Only singlet HC÷TiCl3 was located,and the Mulliken atomic spin densities show that the two single electrons are mostly on the C atom.

关 键 词：B3PW91 reaction mechanism Ti（~3F） CH2=TiCl2 HOTiCl3 

分 类 号：O643.12[理学—物理化学]